Composition of matter and method



Patented June 21, 1938 UNITED STATES COMPOSITION OF MATTER AND lVIETHOD OF MAKING Ernest D Sackett,

signor of one-half to Syracuse,

one-half to Parshad Holding Corporation, New York, and

Corporation, Syracuse,

New York West Somerville, Mass, as-

North American Holding N. Y., a corporation of N. Y., a corporation of No Drawing. Application April 5, 1935, Serial No. 14,799

Claims.

This invention relates to Compositions of matter which are suitable for the filling of the cavity in shoe bottoms intermediate the outer and inner soles and to a method. of preparing the same.

It is an object of this invention to provide a shoe filler composition which shall meet the various conditions and requirements attendant upon the transportation, storage and application of the material to shoe bottoms and which shall 10 so serve its purpose satisfactorily in the finished shoe. It is a further object to provide such a composition from raw materials which are available in adequate quantities and of dependable or controllable properties. It is a further object to provide a composition, the properties of which may be so determined and controlled as to render it suitable for satisfactorily meeting various combinations of requirements, which may arise in View of the conditions under which it may be necessary or desirable to apply the filler composition or under which the finished shoes are to be used. Other objects will appear from the following disclosure.

In all cases of shoe filler compositions, as contrasted with solid filler pieces such as scrap leather, etc., which were formerly employed to fill the shoe sole cavity, it is practically essential that the composition shall be substantially uniform in 'its consistency and other properties. It is also desirable that such uniformity and consistency shall be provided in the composition as first made and that it shall be retained during shipment, storage and use, during application to the shoe and thereafter so long as the shoe is in use.

The consistency has heretofore been provided by mixing a comminuted solid, such as cork, and a viscous fluid or plastic binder, such as rosin and wax tailings, etc. In such compositions the binder presents a certain tendency to flow but this is checked by the mechanical fiow resistance of the comminuted solids. Moreover, the wax tailings possess a relatively sharp melting point and consequently are in the nature of a readily fluid lubricant.

By the present invention it is found that an improved filler composition may be obtainedby employing as a binder for the comminuted-solids or filler, a base material characteristically of uniform composition and consistency, derived from 0 the non-fibrous portion of wood, and more particularly of resinous woods, such as pine, fir, spruce, etc., by steam distillation or destructive distillation, which has been carried to a sufficient temperature and for a sufilcient time substan- 55 tially completely to remove water and all components more volatile than water. This material may be obtained by the direct treatment of resinous wood such as pine stumps or wood waste such as sap. wood, etc., in which case direct or steam 30 distillation may be employed, and in one aspect of the invention redistillation is preferably car ried to a sufficient point to remove rosin and rosin oil, in part or completely. I

It may also be obtained as an indirect by-prod uct of the digestion of wood chips for paper manufacture, by recovery from the spent digester liquors. When derived in this way it contains more or less of the soluble compounds of cellulose. More particularly soda pulp liquor is found to be thus suitable, but probably this is more attributable to the constituents of the wood usually used in this process than to the solvent reagent, and sulfite or sulfate liquors can be similarly employed, if they contain a sufiicient amount of the non-cellulose components of the Wood, by appropriate conversion and elimination of the reagents, such as fites.

Such extractive matter, whether obtained directly by distillation of wood or from wood pulp liquors, is ordinarily dark colored or even black, but is uniformly fluid. and does not contain appreciable free carbon, if any.

erately concentrated sodium hydroxide solution, but may be separated therefrom by further concentration, by evaporation, or by dilution with water, or by acidification.

Preferably, for the extractive matter is liberated from the volaally initially contains. longed dry distillation, with progressively increasing temperatures,-limited, however, to such as cause the charring of the mass, as evidenced by the formation of hard carbon, by lack or loss of fusibility, or by a too high softening or melting point. with certain advantages accruing to the resulting product in consequence, such as a lighter color, by effecting steam distillation'of the extractive matter, instead of by direct ordestructive distillation. j

If the distillation of the raw material is carried sufficiently far, or to a sufficiently high temperature, the rosin may be substantially completely eliminated from the resulting residue. Other Volatile materials I In consequence, the product obtained is relatively stiff and may even be hard and horny at ordinary temperatures. Its softening or melting temperature will be accordingly raised but may be lowered by the addition of rosin and a softer, more fiexible and impressionable donsistency may be afforded by the addition of softening agents. Preferably these are not of a freely fluid solvent character which would be subject to subsequent evaporation or segregation, but are preferably more or less viscous or semi-fluid.

It is also to be noted that a result which is in the sulfides and bisul- It may be readily and substantially completely dissolved in mod-' the purposes of this invention,

tile andfreely liquid components which it usu-' This may be done by pro- A like result may also be reached, and

will likewise be removed.

some ways similar to prolonged distillation may be effected by extracting the residue as usually obtained, with water, dilute caustic alkali, or. other solvent of the more fluid or more reactive components of the residue. The unaffected resi-, due exhibits a stiffer consistency and a somewhat higher softening point. refined residue may then be used with other materials or may be added to a softer residue to give it more resiliency, for use in shoes to. be worn in warmer climates, for example, or where greater resistance to moisture is to be encountered, or in shoes to be worn by those preferring or requiring a stiffer sole-filler composition.

It follows, therefore, that by such procedure of segregating the extractive matter into its higher melting, harder, and generally more inert component and. its more volatile and more reactive components, they may be more definitely recombined or combined with other appropriate materials and the properties and composition of the resulting product accurately provided for in its preparation. It is, of course, thus rendered possible to make stiffer compositions, of higher melting point (and with a lower requirement for fuel, equipment, etc.) than is convenient or practicable by distillation alone. The procedure is also more strictly a separation than is a distillation (especially dry distillation), for it does not entail the application of high temperature which may be accompanied by polymerization, dehydration, decomposition, oxidation, etc. In some instances, however, the latter reactions may be desirable, and in such cases heating and distillation may be effected, the volatile components or byproducts being expelled and the remainder developing, in general, increasingly resistant characteristics as the temperature is raised.

Of course, if distillation is resorted to for separation of the more inert fraction, and more particularly dry or destructive distillation of the extractive matter or residue, it must be arrested short of drastic carbonization. Otherwise a hard, brittle carbon formation will result. Such product may be useful for some purposes, but it is not susceptible to anysubsequent development of fluidity or plasticity or even of formative cohesion and resiliency but only as a hard, solid or a finely comminuted, inert powder.

It may be observed in this connection that if the residue is derived from the distillate obtained by the destructive distillation of wood, it will differ from that obtained when waste liquors from pulp manufacture are employed, in that the latter will contain more or less cellulosic matter and reagent materials, as well as reaction products. However, such components, when present, do not seem topresent any difliculties but may assist in promoting the wide range of variations obtainable in the apparent and effec tive softening of the mass. For example, they blend freely, either by partialsolution or dispersion, or both with aqueous materials generally, but appear to occlude such admixtures within the non-volatile component, so as to prevent subsequent evaporation of the aqueous component.

When waste liquors from paper manufacture are employed as the source of the extractive mat ter herein described and employed, it is ordinarily convenient and desirable, as well as economical, to separate the solvent reagents employed so that these may be recovered and retained for reuse in the pulping operations. This may be done by simply concentrating the liquor, as by evaporation, whereupon the extractive matter Such further distilled or soluble constituents, including the caustic soda,

bi-sulfite or sulfide, as the case may be, may be drawn off in the subnatant solution for reuse in the pulping operation.

The residue may now advantageously be neutralized partially or entirely, or even rendered slightly acidic with a non-voltatile acid such as sulfuric, or a volatile acid such as hydrochloric or acetic, and distilled. 'I'hereupon the volatile components are freed and removed, including water, alcohol, pyroligneous acid, acetone, the various oils and abietic acid or rosin and related substances. Upon standing the abietic acid or rosin crystallizes out from the distillate. The residue from such distillation acquires a relatively thick, viscid consistency, at ordinary temperatures, in contrast to the hard, brittle characteristics of the distilled rosin, for example, and is substantially non-volatile or free from the volatile gaseous and light liquor fractions which have passed over and may be recovered along With the rosin-containing distillate.

The specific characteristics of the residue, in any given instance of practice, may be varied somewhat by the time and the temperature to which the distillation is carried but a product is obtained which is suitable for the purposes of the present invention if the distillation is carried to above the boiling point of water (e. g. to 220 C. to 360 0.) (428 F. to 680 F.) and continued until all of the components vaporizable at that temperature have been removed. Such extractive matter contained in the residue thus. left is practically inert and non-volatile at ordinary atmospheric temperatures. It will usually still contain some rosin, however, which has a melting point varying from below C. to 180 C.

depending upon its purity. For purposes of con- The residue, thus obtained may soften at high- Q er temperatures, approaching 100 F., and exhibits a melting point by the ball and ring method, of to F. These properties may be changed, somewhat, depending upon the temperature and duration of the distillation treatment to which it has been subjected.

Nevertheless, this material is characterized,- especially when prepared by a moderate distillation treatment, to have a low initial melting point,by exhibiting a wide range of melting temperatures between initial softening and complete fluidity. At the same time, it is capable upon being heated to'higher temperatures of becoming freely fluid and of low viscosity. When so prepared as to have a higher initial melting point, the softening range is shorter and at the highertemperatures, while still fluid, it is consistently of greater viscosity also.

The extractive matter as thus derived, is dark brown to black in color and of solid hard consistency, when cold,manifesting brittleness and a semi-conchoidal fracture at very low temperatures. At elevated temperatures, however, it 'is of low viscosity and thin films are transparent or translucent. It is not primarily composed of hydrocarbons. On the contrary, it contains oxygen compounds of high molecular weight which are reactive, especially at elevated temperatures. For example, it manifests the unique characteristic of turning gray or white, in contact with water and loses its plastic or fluid characteristics to a degree but will dissolve in moderately concentrated hot aqueous solutions of caustic soda, almost completely. With slaked or unslaked lime, especially when in molten condition, it reacts violently with evolution of gases and while the product in other respects generally parallels the original material, it is resistant to water and alkaline solvents and is also somewhat firmer or harder, less readilymelted or deformed, and exhibits a distinct resiliency or tendency to return to its original form after deformation.

With such extractive matter it is possible, and within the intended purview of this invention, to develop ultimately a very high degree of stiffness or even solidity of consistency by prolonging the preliminary steam distillation or destructive direct distillation or both. It is also possible, however, and somewhat more convenient, to develop an intermediate degree of hardness or consistency and also a somewhat lower melting point by distillation, and then to develop the additional degree of hardness desired during the preparation of the filler composition, in other ways as will be hereinafter set forth.

The comminuted solids or body materials generally used in shoe filler compositions are suitable in the present invention, and are preferably dry and free from extraneous, inert or powdery materials, such as dust and the like, which may interfere with or reduce the wetting effect or intimate adhesion of the binding material thereto. Comminuted cork is commonly employed and is especially satisfactory for this purpose, though other materials may be used. If the solid material is very porous, or if the binder is for any reason unusually fluid, however, it may be desirable to offset such intimate wetting of the filler granules, as would tend to impregnate them, for example. To effect this result the filler material may be purposely slightly moistened with water, volatile solvent or the like,which will fill the pores, prevent entry of the fluid but more viscous binder, and owing to the temperature of the mass may be subsequently expelled,but as the binder quickly cools and becomes more viscous it is incapable of entering the small pore spaces as the volatile solvent is expelled therefrom.

When the extracted matter is of a consistency which issoft or medium hard, it is heated to such a temperature as to render it fluid and of low viscosity. With material which is more fluid than desired, in the cold, it may be desirable to stiffen it somewhat by the addition of rosin. On the other hand, material of high melting point may have itssoftening temperature lowered by the addition of rosin. Rosin also serves to provide adhesion to the granules and to the shoe bottom and thus prevent slippage. If resin is to be used the two may be mixed together at this stage. The fluidity of the mass is determined by the temperature to which it is heated. The mass may even commence to smoke,but higher temperatures are to be avoided, both to prevent the risk of the batch burning and to correct the tendency of the material to decompose or lose volatile components at such temperatures and thus become too hard, and hence brittle and weak upon cooling.

Preferably, a part of the comminuted body material is next mixed with the remaining constituents of the composition, and the extracted material (with or without rosin) is incorporated therewith, as will be described below. It is found that intimate admixture and uniformity of the ingredients is more surely effected with a small proportion of the body material than it is either without any body material or with the full amount of the body material which is ultimately to be incorporated.

If a more fluid binder has been used than is desirable to have in the finished filler composition, and more especially if it manifests, as a consequence of its original preparation and treatment, an appreciable degree of softening in common solvents such as water, the mixture may be treated at this stage to overcome such effects. It is found that the extracted materials derived from the sources described above, may be improved both in respect of increased viscosity or firmness and in resistance to solvents, by adding to the mass, preferably at such a temperature that it is fairly fluid, the free hydroxide or a weak salt such as the carbonate, of one of the alkaline earth metals. For example, slaked or unslaked or air slaked lime may be used. It is added in dry, finely powdered condition, and thoroughly mixed into the mass. The reaction is rapid and may even be accompanied with explosive violence, when gases are evolved as with the hydroxide and carbonate,-but when more moderate such evolution of gases serves to promote the mixing by making the charge as a Whole lighter and more fluid in respect of the mixing operation. Continued mixing expels the gases, if formed, and the charge becomes uniform. The rest of the comminuted body material may then be added and, by continuing the mixing operation, will be dispersed readily and uniformly throughout the charge as a whole.

The charge as thus obtained is characterized by a Very appreciable tackiness, is resilient to bending and presents a certain measure of elasticity which causes it to return to its original dimensions and shape, but upon rupture it crumbles into an irregular fracture, especially when the proportion of granular body material is high. The particles of the body material are severally separated from one another by the binder and the binder forms a continuous menstruum throughout the mass. It may be sof tened by heat so as to permit the molding, spreading, and adhesion of the composition to cool surfaces. But upon warm smooth surfaces, of high conductivity and low specific heat such as a steel knife or spatula, which may quickly acquire an equivalent temperature by contact with the mass itself, the mass effectively lubricates itself. Moreover, during the heatingoperation, owing to the large proportion of comminuted body material, the mass of the heated composition may retain its original form, under gravity, without flowing, etc. It may therefore be easily handled and again cooled in this condition. As it is to be used and applied to the shoe, however, a suitable amount is separated from the mass, held on a warm steel knife blade and pressed into the shoe cavity. Under such conditions of pressure and the spreading action of the blade, the composition smears over and into the cavity of the shoe, forming an intimate, adhesive contact therewith, while the free surface is readily wiped smooth with a single motion of the knife blade or spatula usually used for the purpose. g

The filled shoe then passes through the subsequent steps of manufacture, while the filler composition cools and reacquires its original consistency at room temperatures. ient; yields to the pressure of the foot of the wearer of the shoe, but does, not permanently deform, as by spreading into other parts of the shoe or by flowing freely. It does soften slightly at the temperature of the human body, or higher temperatures which enhance such softness and improve flexibility. But at lower temperatures or even when very cold, it does not become brittle, nor crack. It does not take up nor give up moisture, and if the shoe is thoroughly wetted, as may happen, it does not dissolve and penetrate the rest of the shoe.

. For example, a batch of extractive material was made by the distillation of acidified soda pulp liquor, as above described, to a melting point of 140145 F. by the ring and ball method, and having a penetration of 4.1 to 7.9 millimeters by a No. 2 penetrometer needle under 50 grs. pressure for five seconds at 77 F. This was employed in the preparation of the following composition:

68 grams distillation residue 1.5 grams Ca(OH)2 5 grams rosin 21-23 grams of comminuted cork (20-30 mesh) or one-half pint by volume The cork was dry and measured by volume, since the absolute density of cork varies and the apparent volume of the amount used,'which ineludes the pore space, is a more definite criterion of the amount of binder required than is the weight. About one-third of the total amount was placed in a small heated mixer having horizontal revolving blades and mixed with the slaked lime. For larger batches the grams may be read pounds in the above formula.

The distillation residue was heated in a separate vessel to a temperature suificient to develop free fluidity, the rosin added and thoroughly incorporated therewith, and the hot, fluid mixture then poured into the portion of the comminuted body material, contained in the mixer, the mixing blades being driven in the usual manner to work the materials into a uniform mass. Active foaming of the mass takes place. This facilitates the mixing operation, which is continued. Eventually the foaming action subsides and the mixture assumes a continuous uniformity, with the granules of body material uniformly distributed therein. The rest of the comminuted body material is then added, and when continued mixing action has effected uniform dispersion of the whole, the charge is finished and may be withdrawn as a more or less crumbly mass of doughy consistency, and is then ready for packing, storage, transportation and use. It may be shaped into loaves, into sheets, or other shapes, as desired. It may also be readily subdivided into the small portions required for filling an individual shoe bottom, even at room temperature. But it is preferable to warm it up slightly, before use, when it both subdivides and spreads and adheres more readily and firmly in the shoe bottom cavity. It is resilient and yieldable at atmospheric temperatures and preserves its characteristics throughout the subsequent operations of shoe manufacture, storage, selling, etc. and finally as the shoe is being worn by the ultimate purchaser, it forms the one part of a shoe which is never worn out.

Certain of the subject matter herein disclosed It is resil but not claimed is now presented and claimed in my copending application Serial No. 162,383, filed September 3, 1937, which is a continuation in part of application Serial No. 39,300 filed September 5, 1935.

I claim:

1. A plastic composition of matter adapted for use in shoe filler compositions, comprising a distillation residue of the substantially neutral, Water-insoluble fraction obtained from the aqueous extract of wood having a volatilization point above 428 F.

2. A shoe filler composition comprising a comminuted body material, and a distillation residue of the substantially neutral, water-insoluble fraction obtained from the aqueous extract of wood, having a volatilization point above the boiling point of water.

3. A shoe filler composition comprising a comminuted body material, and a distillation residue of the substantially neutral, water-insoluble fraction obtained from the aqueous extract of wood, having a volatilization point above 428 F.

4. A shoe filler composition comprising a comminuted body material and a distillation residue of the substantially neutral, water-insoluble fraction obtained from the aqueous extract of wood, having a volatilization point above 680 F.

5. A shoe filler composition comprising a comminuted body material, a distillation residue of the substantially neutral, water-insoluble fraction obtained from the aqueous extract of wood having a volatilization point above the boiling point of water, and. a reaction product'of an alkaline earth metal'therewith.

6. A shoe filler composition comprising a comminuted body material, a distillation residue of the substantially neutral, Waterins01uble'frac tion obtained from the aqueous extract of wood having a volatilization point above 680 F., and

minuted body material, and a distillation residue of the substantially neutral, water-insoluble fraction obtained from the aqueous extract of wood having a volatilization point above 680 F. and the product of reaction of an alkaline compound of an alkaline earth metal therewith.

9. Method of making shoe filler composition comprising mixing a distillation residue of the substantially neutral, water-insoluble fraction obtained from the aqueous extract of wood, having a volatilization point above the boiling point of water, in fluid condition, with comminuted body material.

10. Method of making shoe filler composition comprising mixing a distillation residue of the substantially neutral, water-insoluble fraction obtained from the aqueous extract of wood, having a volatilization point above the boiling point of water, in fluid condition, with comminuted body material, and an alkaline compound of an alkaline earth metal.

' ERNEST D. SACKETT. 

